Organic arseno-phosphorus compounds and process of making same.



Drawing.

UNITED STATES PATENTQFELUE.

ANTOINE MOUINEYRAT, OF PAI -IS, FRANCE.

ORGANIC LB8ENO PHOSPHOBUS COMYOUNDS AND PROCESS OF MAKING SAME.

To all'whom it ma concern:

ANTOINE Mommran, if citizen of the ltepublic of France, and resideiltjof Paris France, (post-oilice {17 Rue Souiilot, Paris, France):

haye invented new and useful Or nic Arsane-Phosphorus Compounds and of'Makirm recesses Same, which process is fully set forth in .e followiu specification.

This invention 'r'ela iae to processes for the preparation of h droxy meta mtr0- phenyl-arsinic acidlan some of its derivatives. 1

ormula of which is wit ou -mat graphically written has been prepared tization, for the amino group of para-arhinophenyl-aminic acid, formula: amen-p m,

graphically written Specification of Letters Patent.

by substituting, b diazophenyl-arsinic Patented July 3, 191'],

Application filed February 18, 1 915. Serial No. 8,686.,

sequent nitration of the iara-hydroXy-phe- 40 nyl-arsinic acid thus obtained, formula:

OH-CQHrAIOIHl,

graphically written a e to Along German Patents No. 205449 of April 25,

190 and No. 224953 of June 10, 1909.)

' The present invention has for its object to rovide a new method of preparing anhy xy-meta-nitrophenyl-arsinic aci startin not with para-aminophenyl-arsinic acid, ut .with fiaramethoxyphenylarsinic acid, (OH,,OC,

AsO,H,) graphically 60 written I r B n 1 6t AIO|B| The latter acid has been obtained-forth; first time by Michaelis, (Liebigs A'rmalen der Ohmic u'nd Pltamacie, vol. 320, p 299-300). To accomplish the desired ject with this acid, the said acid is nitrated in order to obtain the paramethoxy-meta-nitroacid to. graphically written owin to the gresenoe'of the nitro group (N05 when t e latter molecule is heated with an aqueous solution of caustic sodaoru I 1N 08-13 B W y no Eotash, the methfi'l group isflreadily replaced y an atom of y rogen, according to the following equation I Ithasnow been y reducing para-hydroxy-meta-nitroph yl-arsinic acid'withan amalgam of sod in C issolved inan alcoholic solution, (or with cold hydrosulfite of soda), (German PatentNo1221953 of June 10, 1909), para- -hydroxy-meta-aminophenyl-arsinic' acid of he following composition has been obe e l=+ '1' 4 L-estee he" I I foundthat' the latter-acid "can beobt'aine'd much'more readily by the electrolytic reduction of an alkaline aqueous solution of para-hydroxy-meta-nitrophenylarsinic acid; and it has also been found that by the action of oxy-chlorid of phosphorus on para-hydroxy-meta-aminophenyl-arsenic acid, arseno-phosphorus derivatives are obtained, the arsinic radicals of which are slightly toxic and ssess a great spirillicidic and 'trypanos'dmicldic action,

' Ewamuple I,

i arationfof pheny ar'sinic'acid.

11.6grams'of methoxy'phen'ylarsmic acid are dissolvedat 0 C. in 57.5 grams' of ure sulfuric acid; to-this mixture, which is maintained at 0 C.",'there is added, in small portions, a mixture-of 5.1grams of (50% nitric acid and 5 rams of pure sulfuric acid, also at 0 C en the two solutions have beenv well mixed, the vessel containing them is removed from the refrigerating ap-' paratus, and the temperature is allowed to rise to 10 or 12 0.; it is then poured into a 200 cubic centimeters .of'ice water. After soluble, in cold water remaining at rest for ten hours in a cold state, it is filtered in order to separate the crystals of nitm=methoxyphenylarsinic acid which are;-formedreilfhis acid appears 1n the a form, of yellowish hite crystals, hardly 'ore {soluble in hot water, slightly solub e n inethyl alcohol,

acid prepararii ethoxymetanitrosoluble in alkaline solutions givin slightly yellowish salts. These cr stals when heated on latinum oil.

Ethoxy-nitrop enyl-arsinic acid, .formula ocinr-unr-auolm.

eflagrate,

gra hicall written can;

a no;

- l t" H H is prepared in a similar manners Example Ill Preparation of para-hydroxy-meta-nitrophenyl-ar'sinic acid by'starting with para methoxymetanitrophenylarsinicacid. 9

A solution consisting of 10 grams of,

methoxynitrophenylarsinic acid dissolved vin 300 cubic centimeters of 15% aqueous soda solution is heated in a{ water jbath- .The

solution, which is colorless at'the beginning, assumes a, yellow to dark red color as the heating goes on, and at the. end of 5 to 6 hours the reaction is finished. The soiution is allowed to cool and, while cooling, hy-

a droxy-nitrophenyl-arsinic acid is preci itated by a slight excess of hydrochloric acid.

The crystals thus obtained are washed and are :re-crystallized in a suflicient quantity of boiling water. Yellowish-white crystals are thus obtained, which defiagrate when heated on platinum foil; these or stals ossess all the otherproPerties o I faraydroxy ineta-n1trophenyl-ars1nic aci I Example 111. v I, 7 Preparation of parashvdroxy-meta-aininophenyl-arsinic' acid by electrolytic reduction I I ,of para-hydroxy-meta-anitrophenyl-arsinic acid in alkalineaqueous solution.

20 grams of para-hydroxy-meta-nitrotion is placed in a cylindrical glass recep- Ehenyl-arsinic acid are dissolved in '400 one,

1c centimeters of normal soda. This solutacle having a diameter of about ei ht cei iti-z .meters, the bottom of which is fi ledwith" mercur and connected ,with the negativcv pole o a battery of accumulators.

c In said receptacle, there is suspended-a porous vessel, which is closed at its lower part, and WlllCh contains an aqueous solutionof soda rams of soda per liter of 'water) and into t e latter solution a blade of nickel, servin as an anode, is plunged.

In order to avoi heating, the whole apparatus is immersed'in a large vessel contain? ing cold watenx Under-the influence of the electric ".cl'lrrent, the liquid beconies brown on contact" with "the mercury, and, by diflu-t sion, the entire body ,of liqiiid assumes by and bythe same colo tingfl e reduction be bonate.

'colorize it. acid solution of hydroxyaminophenyl-arsinic ingcom leted at the end of about five hours. It will e noted that this reduction is complete when a small portion of filtered liquid no longer gives a precipitate when treated with a slight excess of hydrochloric acid, this being a proof that nomore hydroxynitrophen l-arsinic acid is present.

Throug out-the entire operation, a pressure of 3% to 4 volts is maintained at the terminals, producing a current of 2 amperes.

The reduction being terminated, the cathodic solution is allowed to stand for twenty-four hours, the mercury is separated out, and an exact neutralization is effected by means of hydrochloric acid, taking methyl-orange as an indicator. The solution is then cooled with ice, and after having stood some time, is evaporated in cacao, and. the product obtained therefrom is washed with distilled water. the said product being almost pure para-hydroxy-metaaminophenyl-arsinic acid. The acid thus repared is chocolate brown in color; and to completely purify it, it is re-dissolved in hydrochloric acid and then treated in a heated condition, with animal-black to de- The decolorized hydrochloric acid is then filtered and exactly neutralized with soda. In this manner, pure parahgdroxymetaaminophenylarsinic acid is o tained. I

It has, been observed that phosphorus oxychlorid (F061,) readily reacts with parahydroxmetaaminophenylarsinic acid in the presence ofan aqueoussolution of soda, and produces arseno-phosphorus compoun soluble in aqueous solutions of sodium' car- According to the relative proportions of oxychlorid of phosphorus, sodium carbonate and hydroxy-aminophenylarsinic ,acid used in the operation, arseno-phosphorated compounds of difierent composition are obtained. By way of example, the preparation of a number of these will be given.

Emample I V.

'noplienyl-arsinic' acid cubic cent meters of of caustic soda 23.3 grams of am are dissolved in 30Q water; 90 cubic centimeters at 36 B., and 350 cubic centimeters of 90% alcohol are added, and 27 cubic centimeters of oxychlorid of phosphorus thenintroduced, care being taken that the agitated and cooled. The ized by 18 cubic, centimeters of caustic soda at 36 B., andthen poured into a solution containing 1800 cubic centimeters of water,

- 100 grams of magnesium chlorid and 500 grains of sodium hydrosulfite. -Heating then takes place for four hours at a temperature of 50 C. The precipitate which is formed, is filtered and dried in cacao ove'r sulfuric acid. The product thus obtained a mixture of tetroxydiphosphotetraaminodiwhole ,is suitably liquor is neutralon it a 110; :02

#8 As A. A. X H/WH 11K a H NE NE a K4 w y o and H/WII Elk/NH, n

This is a yellow powder Somme in dilute solutions of sodium carbonate and hydro= chloric acid. p

The alkaline solutions reduce Fehlings solution and the re-agents of Nessler and Tolens. I

In the following examples,the method is the same, but the quantities of caustic soda and oxychlorid ogE phosphorus vary.

Ema/inple V.

Tollens.

Example VI To sums of aminophenyl-arsuiic- ',acid, are added 150. cubic centimeters of caustic sodia at 36 B., and 45 cubic centimeters of oxychl'orid of phospho'rusthen 30 cubic centimeters of caustic soda at 36 are addedto neutralize the liquor.

The product is a yellowish powder which dissolves in dilute solutions of sodium carbonate, and is precipitated therefrom by h d'rochloric acid in which it is insoluble. ts

in dilute hydroalkaline solutions reduce'Fehlin "5 solution and the re-agents of Nessler and ollens.

Ewam/ple VII.

To 23.3 grams of aminophenyl-arsinic acid, are added 180 cubic centimeters of caustic soda at 36 B., and 54 cubic centimeters of oxychlorid of phosphorus; then 36cubic centimeters of caustic soda at 361 B. are added to neutralize the liquor.

The product is a yellowish powder soluble;

Ill dilute solutions of sodium carbonate and insoluble in hydrochloric acid. Its alkaline solutions reduce Fchlings solution and the re-ngents of Nesslel' and Tollens.

What I claim is 1. The herein-described process for the ish powder which is .mg witnesses pounds which comprises the treatment of amino oxych orifd; v;:.

2; The herein-described arseno-phosphorus colnpounds produced by the treatment of amlnophen'ylarsinie acid with phosphorus oxychlorid-and havingz the form of a yellowsbllilfile in dilute solutions of sodium carbonate. r In testimony whereofj I have'si'gned, this specification inthe presence of two subscrib- A. MOUN E YRAT. Witnesses:

DE'Wn'r G. PooLn, Jr M. SEAMLAR.

enyl-erslm acid with phosphorus l I preparation .of erseno-phosphorus com- 

